Thermoplastic elastomer for carbon fiber reinforced plastic bonding lamination

ABSTRACT

The present invention relates to a thermoplastic elastomer for carbon fiber reinforced plastic bonding lamination, which is contained in a layer to be laminated on a layer composed of a carbon-fiber reinforced plastic, wherein the thermoplastic elastomer for carbon fiber reinforced plastic bonding lamination contains a styrene-based thermoplastic elastomer and a polymer modified by an α,β-unsaturated carboxylic acid, the styrene-based thermoplastic elastomer contains components (a) to (d), and a concentration of an α,β-unsaturated carboxylic acid derived from the polymer modified by the α,β-unsaturated carboxylic acid is 0.01 to 10% by mass.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of prior U.S. ApplicationNo. 16/572,077, filed Sep. 16, 2019, the disclosure of which isincorporated herein by reference in its entirety. U.S. Application No.16/572,077 is a continuation application of PCT/JP2018/010320, filedMar. 15, 2018, the disclosure of which is incorporated herein byreference in its entirety. U.S. Application No. 16/572,077 claimspriority to Japanese Application No. 2017-052359, filed Mar. 17, 2017,the disclosure of which is incorporated herein by reference in itsentirety.

TECHNICAL FIELD

The present invention relates to a thermoplastic elastomer which is usedfor bonding lamination between carbon fiber reinforced plastics or as askin in a carbon fiber reinforced plastic laminate and to a laminatedmolded article using the thermoplastic elastomer.

In addition, the present invention relates to an automobile partsstructure, a shipping parts structure, and a power parts structure, eachof which is composed of the aforementioned laminated molded article, andto a bonding method of carbon fiber reinforced plastics.

BACKGROUND ART

Composite materials using a carbon fiber as a reinforced fiber arecalled as carbon fiber reinforced plastics (CFRP) and used forindustrial materials inclusive of aviation members as well as sportsleisure goods, such as golf shafts and tennis rackets, shipping members,and so on. In recent years, such composite materials have also begun tobe put into practical use for automobile parts taking advantage of theircharacteristics of lightweight and strength.

The carbon fiber reinforced plastics are excellent in lightweight andare watched as a substitute for metal; however, in the case where animpact due to strong energy is applied, or in the case where a vibrationis generated due to the impact, there is involved such a drawback thatthe carbon fiber reinforced plastics cannot absorb the energy, so thatthey are broken to pieces. For that reason, the carbon fiber reinforcedplastics are difficult to be applied directly for structural members andso on.

As an improvement thereof, Patent Literature 1 proposes to laminate athermoplastic elastomer layer on a carbon fiber reinforced plastic anddescribes that the thermoplastic elastomer layer contains at least onecrosslinking agent selected from the group of peroxides, amines, and/orbisphenols and is constituted of ethylene propylene rubber (EPM),ethylene propylene diene rubber (EPDM), ethylene acrylate rubber (EAM),fluorocarbon rubber (FCM), acrylate rubber (ACM), acrylonitrilebutadiene rubber (NBR), optionally mixed with polyvinyl chloride (PVC),hydrogenated nitrile rubber (HNBR), carboxylate nitrile rubber (XNBR),hydrogenated carboxylate-nitrile rubber (XHNBR), natural rubber (NR),ethylene vinyl acetate (EVA), chlorosulfonyl polyethylene rubber (CSM),chlorinated polyethylene (CM), butyl rubber (BIIR) or halobutyl rubber,silicone rubber (VMQ, MVQ), fluorosilicone rubber (FVMQ, MFQ),chlorohydrin rubber (CO), epichlorohydrin rubber (ECO), polychloroprenerubber (CR), one-component polyurethane (PU) or a combination or a blendof the aforementioned substances.

BACKGROUND ART LITERATURE Patent Literature

Patent Literature 1: JP-A-2012-523334

SUMMARY OF INVENTION Technical Problem

However, the carbon fiber reinforced plastic/thermoplastic elastomerlaminate exemplified in Patent Literature 1 involves the followingproblems.

Namely, for example, an unreacted epoxy resin is generally impregnatedin a carbon fiber reinforced plastic in a prepreg, and when heated andpressurized in a reaction temperature region of the epoxy resin at thetime of molding, the epoxy resin is solidified and molded as astructure. Meanwhile, when the thermoplastic elastomer is melted at thetime of molding, the molten polymers contribute to bonding to eachother, thereby exhibiting a bonding effect. For this reason, it isdesired that not only the thermoplastic elastomer is basicallyconstituted of components having compatibility or reactivity with theepoxy resin, but also it is melt bonded in a molding temperature regionof the epoxy resin if possible.

However, the melting temperature of a general thermoplastic elastomerdescribed in Patent Literature 1 is high in comparison with the moldingtemperature region of the epoxy resin. Such a thermoplastic elastomer isnot melted at the molding temperature of the epoxy resin, and therefore,there was a case where it is not suited for melt bonding. In addition,it was noted that if there is no reactivity with the epoxy resin, almostall of thermoplastic elastomers are not bonded to the epoxy resin, sothat they are easily peeled off.

Meanwhile, there is a method in which after molding a molded article ofa carbon fiber reinforced plastic is molded, an adhesive is applied tostick a thermoplastic elastomer sheet onto the surface of the carbonfiber reinforced plastic. However, when a structure has a complicatedshape, it is difficult to uniformly apply the adhesive. Additionally,there is such a problem that not only the number of steps increases inproportion to the application of the adhesive, but also the timerequired for production becomes long.

In order to stably maintain the impact resistance of a structurecomposed of a carbon fiber reinforced plastic, even in a complicatedstructure of carbon fiber reinforced plastics, it is required that athermoplastic elastomer sheet can be uniformly stuck with goodadhesiveness, and the resulting structure is stable even after a lapseof time and has high adhesiveness without causing peeling.

However, among the materials constituting the thermoplastic elastomerdescribed in Patent Literature 1, there is included one in which as theperiod of storage is longer, crosslinking of the component of thethermoplastic elastomer used is more likely advanced, and therefore,there was a case where bondability as the thermoplastic elastomer sheetafter long-term storage is not revealed.

Furthermore, from the standpoint of enhancement of a degree of freedomof production, it has been desired to develop a thermoplastic elastomerin which even after storing a thermoplastic elastomer sheet, in moldingusing a typical prepreg, a laminate with a carbon fiber reinforcedplastic can be molded with good adhesiveness without necessity ofaltering the method of construction and also prolonging the moldingtime.

In view of the aforementioned conventional actual situation, the presentinvention has been made. The present invention is aimed to provide athermoplastic elastomer for carbon fiber reinforced plastic bondinglamination, in which lamination molding with a carbon fiber reinforcedplastic can be readily performed; adhesiveness to the carbon fiberreinforced plastic is high; impact resistance of the carbon fiberreinforced plastic can be thoroughly improved through integral moldingwith the carbon fiber reinforced plastic; and even in molding afterlong-term storage, it is possible to perform lamination molding with thecarbon fiber reinforced plastic with good adhesiveness, and also alaminated molded article using this thermoplastic elastomer.

In addition, the present invention is aimed to provide an automobileparts structure, a shipping parts structure, and a power partsstructure, each of which is composed of the aforementioned laminatedmolded article, and also a bonding method of carbon fiber reinforcedplastics.

Solution to Problem

In order to solve the aforementioned problem, the present inventor madeextensive and intensive investigations. As a result, it has been foundthat a thermoplastic elastomer containing a styrene-based thermoplasticelastomer and a polymer modified by an α,β-unsaturated carboxylic acidso as to have a predetermined concentration of an α,β-unsaturatedcarboxylic acid becomes a thermoplastic elastomer which can be readilyintegrally molded with a carbon fiber reinforced plastic even having acomplicated structure, with not only good follow-up properties but alsogood uniformity and adhesiveness and can enhance impact resistance ofthe carbon fiber-forced plastic through lamination, and even afterstorage, its moldability and adhesiveness are not impaired, therebyleading to the present invention.

[1] A thermoplastic elastomer for carbon fiber reinforced plasticbonding lamination, which is contained in a layer to be laminated on alayer composed of a carbon-fiber reinforced plastic,

-   wherein the thermoplastic elastomer for carbon fiber reinforced    plastic bonding lamination contains a styrene-based thermoplastic    elastomer and a polymer modified by an α,β-unsaturated carboxylic    acid,-   the styrene-based thermoplastic elastomer contains the following    components (a) to (d), and-   a concentration of an α,β-unsaturated carboxylic acid derived from    the polymer modified by the α,β-unsaturated carboxylic acid is 0.01    to 10% by mass:-   component (a): a hydrogenated block copolymer which is a    hydrogenated product of an (A)-(B) block copolymer and/or an    (A)-(B)-(A) block copolymer composed of a vinyl aromatic compound    polymer block (A) and a conjugated diene polymer block (B), wherein    at least 80% of double bonds of the conjugated diene moiety of the    conjugated diene polymer block (B) is saturated through    hydrogenation, and a weight average molecular weight thereof is    80,000 to 1,000,000;-   component (b): a softening agent for hydrocarbon-based rubber;-   component (c): a hydrogenated block copolymer composed of an    (A)-(C)-(A) triblock copolymer which is composed of a vinyl aromatic    compound polymer block (A) and a conjugated diene polymer block (C),    wherein the conjugated diene polymer block (C) is constituted of    isoprene; and a part or all of carbon-carbon double bonds based on    isoprene are hydrogenated; and-   component (d): an olefin-based crystalline resin.

The thermoplastic elastomer for carbon fiber reinforced plastic bondinglamination according to [1],

-   wherein based on 100 parts by mass of the sum total of the    component (a) and the component (b), a content of the component (c)    is 20 to 300 parts by mass and a content of the component (d) is 10    to 100 parts by mass; and-   based on 100 % by mass of the sum total of the component (a) and the    component (b), an occupying proportion of the component (a) is 20 to    80% by mass and an occupying proportion of the component (b) is 80    to 20% by mass.

The thermoplastic elastomer for carbon fiber reinforced plastic bondinglamination according to [1] or [2], wherein the polymer modified by theα,β-unsaturated carboxylic acid is a polypropylene modified by a maleicanhydride.

The thermoplastic elastomer for carbon fiber reinforced plastic bondinglamination according to any one of [1] to [3], wherein the component (a)is a hydrogenated block copolymer having a content of the vinyl aromaticcompound polymer block (A) of 10 to 50% by mass.

The thermoplastic elastomer for carbon fiber reinforced plastic bondinglamination according to any one of [1] to [4], wherein the component (c)is a hydrogenated block copolymer in which the content of the vinylaromatic compound polymer block (A) is 10 to 50% by mass, a weightaverage molecular weight is 30,000 to 300,000, and at least 50% ofdouble bonds of the isoprene moiety is saturated through hydrogenation.

The thermoplastic elastomer for carbon fiber reinforced plastic bondinglamination according to any one of [1] to [5], wherein the component (b)is a paraffin-based oil having a weight average molecular weight of 300to 2,000.

The thermoplastic elastomer for carbon fiber reinforced plastic bondinglamination according to any one of [1] to [6], wherein the component (d)is at least one olefin-based crystalline resin selected from the groupconsisting a homopolypropylene, a block polypropylene, and a randompolypropylene, each having a melt flow rate (at 230° C. and a load of21.2 N) of 0.01 to 100 g/10 min.

A laminated molded article containing a layer composed of a carbon fiberreinforced plastic and a thermoplastic elastomer layer composed of athermoplastic elastomer laminated on the carbon fiber reinforcedplastic,

-   wherein the thermoplastic elastomer contains a styrene-based    thermoplastic elastomer and a polymer modified by an α,β-unsaturated    carboxylic acid,-   the styrene-based thermoplastic elastomer contains at least the    following component (c), and-   a concentration of an α,β-unsaturated carboxylic acid derived from    the polymer modified by the α,β-unsaturated carboxylic acid is 0.01    to 10% by mass:-   component (c): a hydrogenated block copolymer composed of an    (A)-(C)-(A) triblock copolymer which is composed of a vinyl aromatic    compound polymer block (A) and a conjugated diene polymer block (C),    wherein the conjugated diene polymer block (C) is constituted of    isoprene, and a part or all of carbon-carbon double bonds based on    isoprene are hydrogenated.

The laminated molded article according to [8],

-   wherein the styrene-based thermoplastic elastomer contains the    following components (a), (b), and (d),-   based on 100 parts by mass of the sum total of the component (a) and    the component (b), a content of the component (c) is 20 to 300 parts    by mass and a content of the component (d) is 10 to 100 parts by    mass, and-   based on 100% by mass of the sum total of the component (a) and the    component (b), an occupying proportion of the component (a) is 20 to    80% by mass and an occupying proportion of the component (b) is 80    to 20% by mass:-   component (a): a hydrogenated block copolymer which is a    hydrogenated product of an (A)-(B) block copolymer and/or an    (A)-(B)-(A) block copolymer composed of a vinyl aromatic compound    polymer block (A) and a conjugated diene polymer block (B), wherein    at least 80% of double bonds of the conjugated diene moiety of the    conjugated diene polymer block (B) is saturated through    hydrogenation, and a weight average molecular weight thereof is    80,000 to 1,000,000;-   component (b): a softening agent for hydrocarbon-based rubber; and-   component (d): an olefin-based crystalline resin.

The laminated molded article according to [8] or [9], wherein thepolymer modified by the α,β-unsaturated carboxylic acid is apolypropylene modified by a maleic anhydride.

The laminated molded article according to [9], wherein the component (a)is a hydrogenated block copolymer having a content of the vinyl aromaticcompound polymer block (A) of 10 to 50% by mass.

The laminated molded article according to any one of [8] to [11],wherein the component (c) is a hydrogenated block copolymer in which acontent of the vinyl aromatic compound polymer block (A) is 10 to 50% bymass, a weight average molecular weight is 30,000 to 300,000, and atleast 50% of double bonds of the isoprene moiety is saturated throughhydrogenation.

The laminated molded article according to [9], wherein the component (b)is a paraffin-based oil having a weight average molecular weight of 300to 2,000.

The laminated molded article according to [9], wherein the component (d)is at least one olefin-based crystalline resin selected from the groupconsisting of a homopolypropylene, a block polypropylene, and a randompolypropylene, each having a melt flow rate (at 230° C. and a load of21.2 N) of 0.01 to 100 g/10 min.

The laminated molded article according to any one of [8] to [14],wherein a sliding material layer is contained on the surface of thethermoplastic elastomer layer on the opposite side to the carbon fiberreinforced plastic.

An automobile parts structure containing the laminated molded articleaccording to any one of [8] to [14].

A shipping parts structure containing the laminated molded articleaccording to any one of [8] to [14].

A power parts structure containing the laminated molded articleaccording to any one of [8] to [14].

A method of bonding a carbon fiber reinforced plastic including using athermoplastic elastomer,

-   wherein the thermoplastic elastomer contains a styrene-based    thermoplastic elastomer and a polymer modified by an α,β-unsaturated    carboxylic acid,-   the styrene-based thermoplastic elastomer contains at least the    following component (c), and-   a concentration of an α,β-unsaturated carboxylic acid derived from    the polymer modified by the α,β-unsaturated carboxylic acid is 0.01    to 10% by mass:-   component (c): a hydrogenated block copolymer composed of an    (A)-(C)-(A) triblock copolymer which is composed of a vinyl aromatic    compound polymer block (A) and a conjugated diene polymer block (C),    wherein the conjugated diene polymer block (C) is constituted of    isoprene, and a part or all of carbon-carbon double bonds based on    isoprene are hydrogenated.

Effects of Invention

The thermoplastic elastomer for carbon fiber reinforced plastic bondinglamination of the present invention can be readily subjected tolamination and integral molding with a carbon fiber reinforced plasticeven having a complicated structure, with not only good follow-upproperties but also good uniformity and adhesiveness and can improveimpact resistance of the carbon fiber reinforced plastic.

Moreover, in the thermoplastic elastomer for carbon fiber reinforcedplastic bonding lamination of the present invention, even afterlong-term storage, its moldability, adhesiveness, and improving effectof impact resistance are not impaired, and these effects can bethoroughly maintained.

DESCRIPTION OF EMBODIMENTS

Although the present invention is hereunder described in detail, but itshould be construed that the following description is an example of theembodiments of the present invention, and the present invention is notlimited to the following explained contents so far as it does notdeviate the spirit thereof, and the present invention can be arbitrarilychanged and carried out within a range where the spirit of the presentinvention is not deviated.

In this description, each expression including “to” interposed betweennumerical values or physical property values means that the rangeincludes the values on both sides of the “to”.

Thermoplastic Elastomer for Carbon Fiber Reinforced Plastic BondingLamination

The thermoplastic elastomer for carbon fiber reinforced plastic bondinglamination of the present invention (hereinafter referred to as“thermoplastic elastomer of the present invention”) is a thermoplasticelastomer which is used as a thermoplastic elastomer of a laminatedmolded article of a carbon fiber reinforced plastic and the foregoingthermoplastic elastomer and is one containing a styrene-basedthermoplastic elastomer and a polymer modified by an α,β-unsaturatedcarboxylic acid, wherein the styrene-based thermoplastic elastomercontains the following components (a) to (d), and a concentration of anα,β-unsaturated carboxylic acid derived from the polymer modified by theα,β-unsaturated carboxylic acid is 0.01 to 10% by mass.

Component (a): A hydrogenated block copolymer which is a hydrogenatedproduct of an (A)-(B) block copolymer and/or an (A)-(B)-(A) blockcopolymer composed of a vinyl aromatic compound polymer block (A) and aconjugated diene polymer block (B) exclusive of isoprene alone, whereinat least 80% of double bonds of the conjugated diene moiety of theconjugated diene polymer block (B) is saturated through hydrogenation,and a weight average molecular weight thereof is 80,000 to 1,000,000;

Component (b): A softening agent for hydrocarbon-based rubber;

Component (c): A hydrogenated block copolymer composed of an (A)-(C)-(A)triblock copolymer which is composed of a vinyl aromatic compoundpolymer block (A) and a conjugated diene polymer block (C), wherein theconjugated diene polymer block (C) is constituted of isoprene, and apart or all of carbon-carbon double bonds based on isoprene arehydrogenated; and

Component (d): An olefin-based crystalline resin.

Component (a): Hydrogenated Block Copolymer

The component (a) which is a constituent component of the styrene-basedthermoplastic elastomer to be used in the present invention is ahydrogenated product of an (A)-(B) block copolymer and/or an (A)-(B)-(A)block copolymer composed of a vinyl aromatic compound polymer block (A)and a conjugated diene polymer block (B) exclusive of isoprene alone,wherein at least 80% of double bonds of the conjugated diene moiety ofthe conjugated diene polymer block (B) is saturated throughhydrogenation, and a weight average molecular weight thereof is 80,000to 1,000,000 (the foregoing hydrogenated block copolymer will behereinafter occasionally referred to as “hydrogenated block copolymer(a)”).

Examples of a vinyl aromatic compound constituting the vinyl aromaticcompound polymer block (A) include one or more of styrene,t-butylstyrene, α-methylstyrene, o-, m-, or p-methylstyrene,1,3-dimethylstyrene, vinylnaphthalene, and vinylanthracene, and styreneand α-methylstyrene are particularly preferred.

Examples of a conjugated diene monomer constituting the conjugated dienepolymer block (B) include one or more of butadiene, 1,3-pentadiene,2,3-dimethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene,4,5-diethyl-1,3-octadiene, and 3-butyl-1,3-octadiene, or a combinationof isoprene and one or more of these conjugated diene monomers, andbutadiene or a mixture of butadiene/isoprene in a mass ratio of 2/8 to6/4 is especially preferred.

In the case where the conjugated diene monomer constituting theconjugated diene polymer block (B) is constituted of only butadiene, ablock copolymer in which a 1,2-addition structure in a microstructure ofthe polybutadiene block is hydrogenated to an extent of 20 to 80% of thewhole is preferred, and a block copolymer in which the 1,2-additionstructure is hydrogenated to an extent of 30 to 60% of the whole isespecially preferred.

The molecular structure of the aforementioned block copolymer of thecomponent (a) may be any of straight-chained, branched, and radialstructures, or a combination thereof.

The component (a) is a hydrogenated block copolymer obtained throughhydrogenation of the aforementioned block copolymer, and itshydrogenation rate is a rate such that a hydrogenation rate of thedouble bond of the conjugated diene moiety of the conjugated dienepolymer block (B) is 80% or more, and preferably 90 to 100%.

In the component (a), the aforementioned wordings “the hydrogenationrate is 80% or more” are synonymous with the aforementioned wordings “atleast 80% of double bonds of the conjugated diene moiety of theconjugated diene polymer block (B) is saturated through hydrogenation”.

The content of the vinyl aromatic compound polymer block (A) in thehydrogenated block copolymer (a) is preferably from 10 to 50% by mass,more preferably from 15 to 45% by mass, and still more preferably from20 to 40% by mass. When the content of the vinyl aromatic compoundpolymer block (A) is less than 10% by mass, mechanical physicalproperties, such as tensile strength, and heat resistance tend to bedeteriorated, whereas when it is more than 50% by mass, flexibility andrubber elasticity are inferior, and bleeding of the component (b) asmentioned later tends to be readily generated.

Although the weight average molecular weight of the hydrogenated blockcopolymer (a) is 80,000 to 1,000,000 in terms of a molecular weight asexpressed in terms of polystyrene through measurement by gel permeationchromatography, it is preferably from 80,000 to 600,000, and morepreferably from 80,000 to 400,000. When the weight average molecularweight is less than 80,000, rubber elasticity and mechanical strengthare lowered, and bleeding of the component (b) as mentioned later isliable to be generated. On the other hand, in the case where the weightaverage molecular weight is more than 1,000,000, fluidity is inferior,and it becomes difficult to perform molding.

As for the production method of the hydrogenated block copolymer (a),any methods may be adopted so long as the aforementioned structure andphysical properties are obtained. For example, a method described in JP40-23798 A; and a method of performing block polymerization in an inertsolvent in the presence of a lithium catalyst can be adopted. Inaddition, the hydrogenation treatment of such a block copolymer can beperformed in an inert solvent in the presence of a hydrogenationcatalyst by a method described in, for example, JP 42-8704 A, JP 43-6636A, JP 59-133203 A, JP 60-79005 A, and so on.

The hydrogenated block copolymer (a) may be a block copolymer in which apolymer molecular chain is extended or branched via a coupling agentresidue. Examples of the coupling agent which is used in this caseinclude diethyl adipate, divinylbenzene, tetrachlorosilicon,butyltrichlorosilicon, tetrachlorotin, butyltrichlorotin,1,2-dibromoethane, 1,4-chloromethylbenzene, bis(trichlorosilyl)ethane,epoxidized linseed oil, tolylene diisocyanate, and 1,2,4-benzenetriisocyanate.

Examples of a commercially available product of the hydrogenated blockcopolymer (a) include products, such as “KRATON-G” (manufactured byKraton Corporation), “SEPTON” (manufactured by Kuraray Co., Ltd.), and“TUFTEC” (manufactured by Asahi Kasei Chemicals Corporation).

The hydrogenated block copolymer (a) may be used alone or may be used inadmixture of two or more thereof having a different block constitutionor physical properties from each other.

Component (b): Softening Agent for Hydrocarbon-based Rubber

The component (b) which is a constituent component of the styrene-basedthermoplastic elastomer to be used in the present invention is asoftening agent for hydrocarbon-based rubber (hereinafter occasionallyreferred to as “softening agent (b) for hydrocarbon-based rubber”).

As the softening agent (b) for hydrocarbon-based rubber, a hydrocarbonhaving a weight average molecular weight of typically from 300 to 2,000,and preferably from 500 to 1,500 is used, and a mineral oil-basedhydrocarbon or a synthetic resin-based hydrocarbon is suitable. Here,the weight average molecular weight is a molecular weight as expressedin terms of polystyrene through measurement by gel permeationchromatography.

In general, the softening agent for mineral oil-based rubber is amixture of an aromatic hydrocarbon, a naphthene-based hydrocarbon, and aparaffin-based hydrocarbon. One in which the proportion of carbon of thearomatic hydrocarbon is 35% by mass or more relative to the total carbonamount is called as an aromatic oil; one in which the proportion ofcarbon of the naphthene-based hydrocarbon is 30 to 45% by mass is calledas a naphthene-based oil; and one in which the proportion of carbon ofthe paraffin-based hydrocarbon is 50% by mass or more is called as aparaffin-based oil. In the present invention, a paraffin-based oil issuitably used.

The softening agent (b) for hydrocarbon-based rubber may be used aloneor may be used in admixture of two or more thereof.

Component (c): Hydrogenated Block Copolymer

The component (c) which is a constituent component of the styrene-basedthermoplastic elastomer to be used in the present invention is composedof an (A)-(C)-(A) triblock copolymer which is composed of a vinylaromatic compound polymer block (A) and a conjugated diene polymer block(C), wherein the conjugated diene polymer block (C) is constituted ofisoprene, and a part or all of carbon-carbon double bonds based onisoprene are hydrogenated (the foregoing hydrogenated block copolymerwill be hereinafter occasionally referred to as “hydrogenated blockcopolymer (c)”).

Similar to the vinyl aromatic compound polymer block (A) in thecomponent (a), examples of a vinyl aromatic compound in the vinylaromatic compound polymer block (A) include styrene, t-butylstyrene,α-methylstyrene, o-, m-, or p-methylstyrene, 1,3-dimethylstyrene,vinylnaphthalene, and vinylanthracene, and styrene and α-methylstyreneare particularly preferred.

The monomer constituting the conjugated diene polymer block (C) isisoprene.

The molecular structure of the aforementioned block copolymer of thecomponent (c) may be any of straight-chained, branched, and radialstructures, or a combination thereof.

The component (c) is a hydrogenated block copolymer obtained throughhydrogenation of the aforementioned block copolymer, and itshydrogenation rate is a rate such that a hydrogenation rate of thedouble bond of the isoprene moiety of the conjugated diene polymer block(C) is preferably 50% or more, and more preferably from 70 to 100%.

In the component (c), the aforementioned wordings “the hydrogenationrate is 50% or more” are synonymous with the aforementioned wordings “atleast 50% of double bonds of the isoprene moiety is saturated throughhydrogenation”.

The content of the vinyl aromatic compound polymer block (A) in thehydrogenated block copolymer (c) is preferably from 10 to 50% by mass,more preferably from 15 to 40% by mass, and still more preferably from15 to 35% by mass. When the content of the vinyl aromatic compoundpolymer block (A) is less than 10% by mass, mechanical physicalproperties, such as tensile strength, and heat resistance tend to bedeteriorated, whereas when it is more than 50% by mass, flexibility andrubber elasticity are inferior, and bleeding of the aforementionedcomponent (b) tends to be easily generated.

The weight average molecular weight of the hydrogenated block copolymer(c) is preferably from 30,000 to 300,000, and more preferably from50,000 to 250,000 in terms of a molecular weight as expressed in termsof polystyrene through measurement by gel permeation chromatography.When the weight average molecular weight is less than 30,000, rubberelasticity and mechanical strength are lowered, and bleeding of theaforementioned component (b) is liable to be generated. On the otherhand, in the case where the weight average molecular weight is more than300,000, fluidity is inferior, and it becomes difficult to performmolding.

The hydrogenated block copolymer (c) can be produced in the same methodas in the aforementioned component (a).

Examples of a commercially available product of the hydrogenated blockcopolymer (c) include products, such as “HYBRAR” (manufactured byKuraray Co., Ltd.).

The hydrogenated block copolymer (c) may be used alone or may be used inadmixture of two or more thereof having a different block constitutionor physical properties from each other.

Component (d): Olefin-based Crystalline Resin

When the styrene-based thermoplastic elastomer which is used in thepresent invention contains an olefin-based crystalline resin as thecomponent (d) to an extent of not affecting the adhesiveness, the heatresistance can be enhanced.

Examples of the olefin-based crystalline resin of the component (d)(hereinafter occasionally referred to as “olefin-based crystalline resin(d)”) include an ethylene homopolymer, a copolymer of ethylene and anα-olefin or a vinyl monomer, such as vinyl acetate and ethyleneacrylate, a propylene homopolymer, a block copolymer of propylene and anα-olefin, a random copolymer of propylene and an α-olefin, a 1-butenehomopolymer, a random copolymer of 1-butene and an α-olefin, a4-methyl-1-pentene homopolymer, and a random copolymer of4-methyl-1-pentene and an α-olefin. Examples of other α-olefin as acomonomer include ethylene, 1-butene, 4-methyl-1-pentene, 1-hexene, and1-octene, and one or more of these can be selected and used.

Among these olefin-based crystalline resins (d), from the viewpoint ofheat resistance and compatibility, a crystalline polypropylene resin ispreferred, and a polypropylene-based resin, such as homopolypropylene,block polypropylene, and random polypropylene, is more preferred.

As for the olefin-based crystalline resin (d), its melt flow rate (MFR)measured under a condition at 230° C. and a load of 21.2 N in conformitywith a method described in JIS K7210 is preferably from 0.01 to 100 g/10min, and more preferably from 0.1 to 70 g/min. In the case of using one,the MFR of which is less than the aforementioned lower limit, thefluidity is inferior, so that there is a tendency that it becomesdifficult to perform molding, whereas in the case of using one, the MFRof which is more than the aforementioned upper limit, the melt viscositydecreases, and there is a tendency that it becomes difficult to performsheet molding.

The olefin-based crystalline resin (d) may be used alone or may be usedin admixture of two or more thereof having a different monomercomposition or physical properties from each other.

Content Ratio of Components (a) to (d)

It is preferred that the styrene-based thermoplastic elastomer which isused in the present invention contains the aforementioned components (a)to (d), and based on 100 parts by mass of the sum total of the component(a) and the component (b), a content of the component (c) is 20 to 300parts by mass, and a content of the component (d) is 10 to 100 parts bymass.

When the content of the component (c) is more than the aforementionedupper limit, bleeding of the oil is generated, stickiness increases, andworkability is worsened, whereas when it is less than the aforementionedlower limit, bondability to the carbon fiber reinforced plastic isworsened. The content of the component (c) is more preferably from 40 to200 parts by mass based on 100 parts by mass of the sum total of thecomponent (a) and the component (b).

As mentioned above, when the component (d) is contained, heat resistancecan be enhanced. When the content of the component (d) is theaforementioned lower limit or more, this effect can be satisfactorilyobtained, whereas when it is more than the aforementioned upper limit,adhesiveness is inferior, and flexibility is worsened. The content ofthe component (d) is more preferably from 10 to 80 parts by mass basedon 100 parts by mass of the sum total of the component (a) and thecomponent (b).

As for a constitution ratio of the component (a) and the component (b),based on 100% by mass of the sum total of these components, it ispreferred that the content of the component (a) is 20 to 80% by mass,and the content of the component (b) is 80 to 20% by mass, and it ismore preferred that the content of the component (a) is 25 to 75% bymass, and the content of the component (b) is 75 to 25% by mass. Whenthe content of the component (a) is smaller, and the content of thecomponent (b) is larger than the foregoing range, heat resistance of theobtained thermoplastic elastomer is possibly inferior, or bleeding ispossibly generated. On the other hand, when the content of the component(a) is larger, and the content of the component (b) is smaller than theforegoing range, flexibility and molding processability are worsened.

Polymer Modified by α,β-Unsaturated Carboxylic Acid

Examples of an α,β-unsaturated carboxylic acid as a modifier of thepolymer modified by the α,β-unsaturated carboxylic acid, which iscontained in the thermoplastic elastomer of the present invention,include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid,fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid,crotonic acid, and isocrotonic acid. As the modifier, a derivative ofsuch as α,β-unsaturated carboxylic acid may be used, and examples of thederivative include an acid anhydride or an ester of such anα,β-unsaturated carboxylic acid. Furthermore, the derivative may be aderivative, such as an acid halide, an amide, and an imide. Among these,maleic acid or an anhydride thereof is especially suitable.

As a polymer of a base material for modification of the polymer modifiedby the α,β-unsaturated carboxylic acid, a polyolefin is desired.Examples thereof include homopolymers of an α-olefin having 2 or morecarbon atoms, such as ethylene, propylene, butene-1, hexene-1,3-methylbutene-1, 4-methylpentene-1, heptene-1, octene-1, and decene-1;random or block copolymers of two or more of these monomers; random,block, or graft copolymers of, as a main component, an α-olefin having 2or more carbon atoms and other monomer; and mixtures thereof. Thepolyolefin is especially preferably an ethylene-based resin or apropylene-based resin having a melt flow rate in conformity with JISK7210 (MFR: In a case of a resin containing ethylene as a maincomponent, measured under a condition at 190° C. and a load of 21.2 N,and in a case of a resin containing propylene as a main component,measured under a condition at 230° C. and a load of 21.2 N) of from 0.01to 200 g/10 min, and preferably from 0.1 to 100 g/10 min. The polymermodified by the α,β-unsaturated carboxylic acid is most preferablypolypropylene modified by maleic anhydride.

It is preferable that the polymer modified by the α,β-unsaturatedcarboxylic acid which is used in the present invention is a polymer inwhich the α,β-unsaturated carboxylic acid is grafted in a ratio rangingfrom 0.1 to 20 parts by mass, especially from 0.2 to 10 parts by mass,based on the 100 parts by mass of the polymer, namely a polymer modifiedby an α,β-unsaturated carboxylic acid in which a modification rate bythe α,β-unsaturated carboxylic acid is 0.1 to 20% by mass, especially0.2 to 10% by mass, based on 100% by mass of the polymer. When thismodification rate is less than 0.1% by mass, a thermoplastic elastomerhaving satisfactory bondability cannot be produced, whereas when it ismore than 20% by mass, incorporation of an unreacted material or aby-product increases, and bondability is lowered.

The modification rate by the α,β-unsaturated carboxylic acid of thepolymer modified by the α,β-unsaturated carboxylic acid can be confirmedby, for example, 1H-NMR, IR absorption spectroscopy, ICP atomic emissionspectroscopy with a high-frequency plasma emission analyzer, or thelike. Namely, for example, in the case where the α,β-unsaturatedcarboxylic acid is maleic acid, the modification rate can be determinedby measuring absorption inherent to maleic acid in a sample prepared bypress molding in a sheet form having a thickness of about 100 µm,specifically carbonyl characteristic absorption at 1,900 to 1,600 cm⁻¹(C=O stretching vibration band).

The amount of the α,β-unsaturated carboxylic acid in the polymermodified by the α,β-unsaturated carboxylic acid as measured in this wayis a sum total of the amount of the α,β-unsaturated carboxylic acidgrafted in the polymer of the base material for modification of thepolymer modified by the α,β-unsaturated carboxylic acid and theα,β-unsaturated carboxylic acid component which is not grafted in thispolymer. In the present invention, the sum total of the α,β-unsaturatedcarboxylic acid grafted in the polymer of the base material formodification as measured by the aforementioned measurement method andthe non-grafted α,β-unsaturated carboxylic acid component is defined asthe amount or modification rate of the α,β-unsaturated carboxylic acid.

The production method of the polymer modified by the α,β-unsaturatedcarboxylic acid is not particularly limited; and the modification methodis not particularly limited, and a solution modification method ofundergoing the reaction in an organic solvent, or a melt modificationmethod of undergoing modification can be used.

Such a polymer modified by the α,β-unsaturated carboxylic acid may beused alone, or may be used by mixing with an α,β-unsaturated carboxylicacid as a modifier or a base material polymer for modification, or inadmixture of two or more thereof having a different modification ratefrom each other.

The thermoplastic elastomer of the present invention is one prepared byblending the aforementioned styrene-based thermoplastic elastomer withthe polymer modified by the α,β-unsaturated carboxylic acid such thatthe concentration of the α,β-unsaturated carboxylic acid (content of theα,β-unsaturated carboxylic acid) derived from the polymer modified bythe α,β-unsaturated carboxylic acid in the thermoplastic elastomer is0.01 to 10% by mass.

When the concentration of the α,β-unsaturated carboxylic acid is lessthan 0.01% by mass, adhesiveness to the carbon fiber reinforced plasticis inferior, and satisfactory bondability cannot be obtained, whereaswhen it is more than 10% by mass, bondability is lowered. Theconcentration of the α,β-unsaturated carboxylic acid of thethermoplastic elastomer of the present invention is preferably from 0.01to 8% by mass, and more preferably from 0.01 to 6% by mass.

Organic Peroxide

The thermoplastic elastomer of the present invention can be produced byheat mixing the aforementioned components (a) to (d) and the polymermodified by the α,β-unsaturated carboxylic acid by using a mixingmachine, such as an extruder, and on that occasion, a crosslinkingtreatment may be performed by mixing an organic peroxide or acrosslinking assistant.

Specifically, examples of the organic peroxide include dimethylperoxide, di-t-butyl peroxide,2,5-dimethyl-2,5-di-(t-butylperoxy)hexane,2,5-dimethyl-2,5-di-(t-butylperoxy)hexyne-3,1,3-bis(t-butylperoxyisopropyl)benzene,1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl4,4-bis(t-butylperoxy)valerate, benzoyl peroxide, p-chlorobenzoylperoxide, 2,4-dichlorobenzoyl peroxide, t-butyl peroxybenzoate, t-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, andt-butylcumyl peroxide, and 2,5-dimethyl-2,5-di-(t-butylperoxy)hexane,2,5-dimethyl-2,5-di-(t-butylperoxy)hexyne-3,1,3-bis(t-butylperoxyisopropyl)benzene,1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, and n-butyl4,4-bis(t-butylperoxy)valerate are preferred. These organic peroxidescan be used either alone or in admixture of two or more thereof.

The organic peroxide is used in an amount ranging typically from 0.05 to3 parts by mass, and preferably from 0.1 to 2 parts by mass, based on100 parts by mass of the sum total of the components (a) to (d).

On the occasion of the crosslinking treatment with such an organicperoxide, assistants for peroxy crosslinking, such as sulfur, p-quinonedioxime, p,p′-dibenzoyl quinone dioxime, N-methyl-N-4-dinitrosoaniline,nitrosobenzene, diphenylguanidine, andtrimethylolpropane-N,N′-m-phenylenedimaleimide; polyfunctionalmethacrylate monomers, such as divinylbenzene, triallyl cyanurate,ethylene glycol dimethacrylate, diethylene glycol dimethacrylate,polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate,and ally methacrylate; and polyfunctional vinyl monomers, such as vinylbutyrate and vinyl stearate, can be blended.

The aforementioned crosslinking assistant, polyfunctional methacrylate,or polyfunctional polyvinyl polymer is used in an amount of typicallyfrom 0.1 to 5 parts by mass, and preferably from 0.2 to 4 parts by mass,based on 100 parts by mass of the sum total of the components (a) to(d).

Other Components

The thermoplastic elastomer of the present invention may be blended withvarious additives, such as a stabilizer, a lubricant, an antioxidant, aUV absorber, a foaming agent, a flame retardant, a colorant, and afiller, or other thermoplastic resin other than the essentialcomponents, or rubber, as the need arises.

Among these, in particular, it is preferred to add an antioxidant as thestabilizer. Examples of the antioxidant include monophenol-based,bisphenol-based, tri- or more polyphenol-based, thiobisphenol-based,naphthylamine-based, diphenylamine-based, and phenylenediamine-basedantioxidants. Among these, monophenol-based, bisphenol-based, tri- ormore polyphenol-based, and thiobisphenol-based antioxidants arepreferred. In the case of blending the antioxidant, its addition amountis typically from 0.01 to 5 parts by mass, and preferably from 0.05 to 3parts by mass, based on 100 parts by mass of the sum total of thecomponents (a) to (d). When this addition amount is less than 0.01 partsby mass, the effect of the antioxidant is hardly obtained, and even whenit is more than 5 parts by mass, an enhancement effect corresponding tothe addition amount is not obtained, and such is not preferred from thestandpoint of cost.

Examples of the thermoplastic resin other than the essential componentsinclude polyphenylene ether-based resins; polyamide-based resins, suchas nylon 6 and nylon 66; polyester-based resins, such as polyethyleneterephthalate and polybutylene terephthalate; polyoxymethylene-basedresins, such as a polyoxymethylene homopolymer and a polyoxymethylenecopolymer; polymethyl methacrylate-based resins; polystyrene-basedresins; biodegradable resins; and vegetable-derived raw material resins.

Examples of the rubber include olefin-based rubbers, such as anethylene/propylene copolymer rubber and anethylene/propylene/non-conjugated diene copolymer rubber; polybutadienerubbers; and styrene-based copolymer rubbers other than the essentialcomponents.

Production Method of Thermoplastic Elastomer

The thermoplastic elastomer of the present invention is produced throughheat kneading of a blend of the thermoplastic elastomer containing thecomponent (a): hydrogenated block copolymer, the component (b):softening agent for hydrocarbon-based rubber, the component (c):hydrogenated block copolymer, the component (d): olefin-basedcrystalline resin, the polymer modified by the α,β-unsaturatedcarboxylic acid, and further optionally, the organic peroxide, thecrosslinking assistant, and the various additives.

In the production of the thermoplastic elastomer of the presentinvention, a Henschel mixer, a ribbon blender, a V-type blender, and thelike are used as a mixing device; and a mixing roll, a kneader, aBanbury mixer, a Brabender Plastograph, a single screw extruder, atwin-screw extruder, and the like are used as a kneading device.

Molding of Thermoplastic Elastomer

The thermoplastic elastomer of the present invention can be molded by amolding machine, such as an injection molding machine, a single screwextrusion molding machine, a twin-screw extrusion molding machine, acompression molding machine, and a calendar processing machine, and bycomplexing a molded product thereof with a prepreg CFRP throughlamination and integral molding, various structures can be obtained.

Laminated Molded Article

The laminated molded article of the present invention is one including alayer composed of a carbon fiber reinforced plastic; and a thermoplasticelastomer layer composed of a thermoplastic elastomer X laminated on thecarbon fiber reinforced plastic.

The thermoplastic elastomer X contains a styrene-based thermoplasticelastomer and the aforementioned polymer modified by the α,β-unsaturatedcarboxylic acid, wherein the styrene-based thermoplastic elastomercontains at least the aforementioned compound (c), and the concentrationof the α,β-unsaturated carboxylic acid derived from the polymer modifiedby the α,β-unsaturated carboxylic acid is 0.01 to 10% by mass.

It is preferable that the thermoplastic elastomer X is theaforementioned thermoplastic elastomer of the present invention.

The laminated molded article of the present invention may be one inwhich the thermoplastic elastomer layer is laminated as an intermediatelayer between the carbon fiber reinforced plastic and the carbon fiberreinforced plastic, and may also be one in which the thermoplasticelastomer layer is laminated as a skin on the carbon fiber reinforcedplastic.

The laminated molded article of the present invention may also be one inwhich a layer of a sliding material is further laminated on theaforementioned thermoplastic elastomer layer laminated on the carbonfiber reinforced plastic, namely one in which a sliding material layeris contained on the surface of the aforementioned thermoplasticelastomer layer on the opposite side to the aforementioned carbon fiberreinforced plastic.

As the carbon fiber reinforced plastic, although a carbon fiberreinforced epoxy resin is typically used, it should be construed thatthe resin species of the carbon fiber reinforced plastic is by no meanslimited to the epoxy resin. In addition, commercially available productscan be used as the carbon fiber reinforced plastic, and the carbon fiberreinforced plastic may be either a single kind or a combination of twoor more different kinds.

The layer composed of a carbon fiber reinforced plastic can be obtainedby using the aforementioned carbon fiber reinforced plastic.

As the sliding material which is used for the surface layer,silane-crosslinked polyethylene and so on can be used.

In such a laminated molded article of the present invention, its impactresistance is significantly improved owing to the thermoplasticelastomer laminated on the carbon fiber reinforced plastic with goodadhesiveness, and it is possible to apply the laminated molded articleof the present invention in a wide range of fields inclusive of anautomobile parts structure of every sort as well as a shipping partsstructure, a power parts structure, a building parts structure, and soon. Above all, the laminated molded article of the present invention issuitably used for an automobile application which is eagerly desired toachieve lightweight, and in such an application, the effect forimproving the impact resistance according to the present invention isthoroughly exhibited.

Bonding Method of Carbon Fiber Reinforced Plastic

The bonding method of the carbon fiber reinforced plastic of the presentinvention is a method of bonding the carbon fiber reinforced plastic byusing the aforementioned thermoplastic elastomer X.

Specifically, the foregoing bonding method is a method in which by usingthe layer composed of the carbon fiber reinforced plastic and thethermoplastic elastomer layer composed of the aforementionedthermoplastic elastomer X, the thermoplastic elastomer layer composed ofthe thermoplastic elastomer X is laminated on the layer composed of thecarbon fiber reinforced plastic through thermal press bonding or thelike for 1 to 5 hours under a condition at 70 to 250° C. and a pressureof 0.1 to 1.0 MPa, by which the resulting layer works as an adhesivelayer, and a separate layer composed of other base material (inclusiveof the layer composed of the carbon fiber reinforced plastic) is furtherbonded thereon.

EXAMPLES

Although the present invention is hereunder described in more detail byreference to Examples, it should be construed that the present inventionis not limited to the following Examples so long as it does not deviatethe spirit thereof. The values of the various production conditions andevaluation results in the following Examples mean preferred values ofthe upper or lower limits in embodiments of the present invention, and apreferred range may be a range defined by the aforementioned upper limitor lower limit value and either the value in the Example or acombination of the values in the Examples.

Raw Materials

The following raw materials were used in the following several Examples.

Component (a): Hydrogenated Block Copolymer

SEBS-1: Hydrogenated product of copolymer of (styrene block)-(butadieneblock)-(styrene block)

-   Styrene content: 33% by mass-   Hydrogenation rate: 98% or more-   Weight average molecular weight: about 260,000

SEBS-2: Hydrogenated product of copolymer of (styrene block)-(butadieneblock)-(styrene block)

-   Styrene content: 29% by mass-   Hydrogenation rate: 98% or more-   Weight average molecular weight: about 90,000

Component (b): Softening Agent for Hydrocarbon-based Rubber

OIL-1: Paraffin-based oil (“Diana Process Oil PW-90”, manufactured byIdemitsu Kosan Co., Ltd.)

-   Weight average molecular weight: 550-   Kinematic viscosity at 40° C.: 96 mm²/sec

Component (c): Hydrogenated Block Copolymer

SEPS-1: Hydrogenated product of copolymer of (styrene block)-(isopreneblock)-(styrene block)

-   Styrene content: 20% by mass-   Hydrogenation rate: 98% or more-   Weight average molecular weight: about 100,000

Component (d): Olefin-based Crystalline Resin

-   PP-1: Propylene homopolymer (manufactured by Japan Polypropylene    Corporation)-   Melt flow rate: 5 g/10 min (at 230° C. and a load of 21.2 N)-   PP-2: Propylene/ethyl random copolymer (manufactured by Japan    Polypropylene Corporation)-   Melt flow rate: 1 g/10 min (at 230° C. and a load of 21.2 N)

Polymer Modified by α,β-Unsaturated Carboxylic Acid

-   MAH-PP: Polypropylene modified by Maleic anhydride-   Maleic anhydride content (modification rate): 1.0% by mass

Evaluation Method of Thermoplastic Elastomer

Various evaluation methods of the thermoplastic elastomers in theExamples and Comparative Examples are shown below.

In the measurement of the following (2), each of the thermoplasticelastomers was injection molded with an injection molding machine of anin-line screw type (a product No.: IS130, manufactured by ToshibaMachine Co., Ltd.) under a condition at an injection pressure of 50 MPa,a cylinder temperature of 220° C., and a die temperature of 40° C.,thereby molding a sheet of 2 mm in thickness × 120 mm in width × 80 mmin length.

In the tensile test of the following (3), a dumbbell-shaped test piecewas punched out from the obtained sheet (2 mm in thickness × 120 mm inwidth × 80 mm in length) by using a test piece punching blade (JIS No.3, dumbbell-shaped) in conformity with JIS K6251, and the measurementwas performed by using this test piece.

Melt Flow Rate (MFR)

The measurement was performed at 230° C. and a load of 21.2 N inconformity with JIS K7210.

Durometer Hardness A

The hardness (after 15 seconds) was measured in conformity with JISK6253 (JIS-A).

Tensile Strength at Break/Elongation at Break (Tensile Test)

The measurement was performed at a testing rate of 500 mm/min inconformity with JIS K6251.

Evaluation Method of Thermoplastic Elastomer Sheet Maximum Peel Strength

The thermoplastic elastomer sheet obtained in each Example wassandwiched between two sheets of prepregs of CFRP having an epoxy resinimpregnated therein (20 cm in square and 0.35 mm in thickness), and theresultant was subjected to thermal press bonding in an autoclave at 130°C. and a pressure of 0.5 MPa for 4 hours, thereby obtaining a laminatedmolded article having the thermoplastic elastomer sheet laminatedbetween the CFRP sheets.

One of the CFRP sheets and the thermoplastic elastomer sheet of theobtained laminated molded article were notched in a width of 25 mm byusing a cutter; the other CFRP sheet was peeled off from thethermoplastic elastomer; an end of that CFRP sheet and an end of thelaminate of the CFRP sheet and the thermoplastic elastomer sheet wereeach installed in a chuck of an autograph; and peeling was performed at180°, thereby the maximum peel strength was measured.

Maximum Peel Strength after Long-Term Storage

After allowing the thermoplastic elastomer sheet obtained in eachExample to stand at room temperature for 3 months, a laminated moldedarticle was prepared in the same manner as in the laminated moldedarticle in the aforementioned evaluation of maximum peel strength, andthe obtained laminated molded article was measured for the maximum peelstrength at 180° in the same manner as in the aforementioned evaluationof maximum peel strength.

Impact Test

On the sheet surface of a laminated molded article prepared in the samemanner as in the laminated molded article in the aforementionedevaluation of maximum peeling strength, 1 kg of a weight was allowed tofall down on a ball of ϕ0.625 inch from a height of 30 cm at ordinarytemperature by using a Du Pont impact tester, and a crack condition ofthe laminated molded article was evaluated according to the followingcriteria.

As Comparative Example 2, a laminated molded article was obtained in thesame manner as in the aforementioned maximum peel strength, except thatthe thermoplastic elastomer sheet was not used, and only the prepreg ofCFRP was used, and this laminated molded article made of only the CFRPwas similarly subjected to the impact test and evaluated.

-   A: The CFRP sheet remained without being cracked.-   B: The CFRP sheet was cracked.

Overall Evaluation

The overall evaluation was made on a basis of the aforementioned resultsaccording to the following criteria.

-   A: The maximum peel strength and the maximum peel strength after    long-term storage were 10.0 N/cm or more, and the CFRP sheet    remained without being cracked in the impact test.-   B: The maximum peel strength and the maximum peel strength after    long-term storage were 1.0 N/cm or more and less than 10.0 N/cm, and    the CFRP sheet remained without being cracked in the impact test.-   C: The maximum peel strength and the maximum peel strength after    long-term storage were less than 1.0 N/cm, and the CFRP sheet    remained without being cracked in the impact test.-   D: The maximum peel strength and the maximum peel strength after    long-term storage were less than 1.0 N/cm, and the CFRP sheet was    cracked.

Examples 1 to 5 and Comparative Example 1 Preparation of ThermoplasticElastomer

To a blend preparation shown in Table 1, 0.1 parts by mass of, as astabilizer,tetrakis[methylene-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane(“IRGANOX 1010”, manufactured by Ciba Specialty Chemicals) was added,and the contents were mixed with a Henschel mixer, and the mixture wasthen extruded with a twin-screw extruder “TEX 30”, manufactured by JSWat 210° C. and a screw of a rotation rate of 400 rpm by using a weightfeeder, thereby obtaining each of thermoplastic elastomers.

Preparation of Thermoplastic Elastomer Sheet

Each of the obtained thermoplastic elastomers was press molded with apress under a condition at a temperature of 200° C., thereby preparing athermoplastic elastomer sheet having a thickness of 1 mm.

Using each of the obtained thermoplastic elastomer sheets, theaforementioned evaluations were performed. The results are shown inTable 1.

TABLE 1 Example Comparative Example 1 2 3 4 5 1 2 Styrene-basedthermoplastic elastomer Component (a) SEBS-1 (parts by mass) - - - 5050 - - SEBS-2 (parts by mass) 40 40 40 - - 40 - Component (b) OIL-1(parts by mass) 60 60 60 50 50 60 - Component (c) SEPS-1 (parts by mass)80 105 105 170 170 - - Component (d) PP-1 (parts by mass) 40 40 30 - -20 - PP-2 (parts by mass) - - - 60 55 - - Polymer modified byα,β-unsaturated carboxylic acid MAH-PP Concentration of maleic anhydridein thermoplastic elastomer composition (% by mass) 0.03 0.03 0.05 0.020.03 0.03 - MFR (at 230° C., load: 21.2 N) g/10 min 18.0 15.4 19.7 8.69.3 8.0 - Durometer hardness A (after 15 seconds) - 68 65 62 68 68 72 -Tensile strength at break MPa 7.2 10.6 9.9 13.3 12.9 11.8 - Elongationat break % 780 865 940 800 800 960 - Evaluation results of thermoplasticelastomer sheet Maximum peel strength N/cm 7.1 13.6 8.8 11.5 13.1 0.2 -Maximum peel strength after long-term storage N/cm 7.2 14.6 8.7 11.813.5 0.2 - Impact test A A A A A A B Overall judgement B A B A A C D

From Table 1, it is noted that according to the thermoplastic elastomerof the present invention obtained in each of Examples 1 to 5; thebonding lamination with the carbon fiber reinforced plastic can beeasily performed; the laminated molded article with high adhesivenesscan be obtained; and the impact resistance of the carbon fiberreinforced plastic can be significantly improved. In addition, it isnoted that according to the thermoplastic elastomer of the presentinvention obtained in each of Examples 1 to 5, the carbon fiberreinforced plastic laminated article which is able to secure theadhesiveness and has high adhesiveness, even in molding after long-termstorage, and hence, is usable for an endurance application can beprovided.

In contrast, the laminated molded article of Comparative Example 2 inwhich the thermoplastic elastomer of the present invention is notlaminated is poor in the impact resistance. In Comparative Example 1which does not contain the component (c) in the thermoplastic elastomer,the adhesiveness to CFRP is poor.

While the present invention has been described in detail and withreference to specific embodiments thereof, it will be apparent to oneskilled in the art that various changes and modifications can be madetherein without departing from the spirit and scope thereof. The presentapplication is based on a Japanese patent application filed on Mar. 17,2017 (Japanese Patent Application No. 2017-052359), the entireties ofwhich are incorporated by reference.

1. A laminated molded article, comprising: a layer of a carbon fiberreinforced plastic; and a layer of a thermoplastic elastomer; whereinthe thermoplastic elastomer comprises a styrene-based thermoplasticelastomer and a polymer modified by an α,β-unsaturated carboxylic acid,and the styrene-based thermoplastic elastomer comprises: an (A)-(C)-(A)triblock copolymer (c) having a vinyl aromatic compound polymer block(A) and a conjugated diene polymer block (C), wherein the conjugateddiene polymer block (C) is constituted of isoprene, and a part or all ofcarbon-carbon double bonds based on isoprene are hydrogenated.
 2. Thelaminated molded article according to claim 1, wherein the polymermodified by the α,β-unsaturated carboxylic acid comprises a polyolefinmodified by the a,β-unsaturated carboxylic acid.
 3. The laminated moldedarticle according to claim 2, wherein the polyolefin modified by theα,β-unsaturated carboxylic acid comprises a polypropylene modified bymaleic anhydride.
 4. The laminated molded article according to claim 1,wherein the styrene-based thermoplastic elastomer further comprises: (a)a hydrogenated (A)-(B) block copolymer and/or a hydrogenated (A)-(B)-(A)block copolymer; wherein block (A) is composed of a vinyl aromaticcompound, block (B) is composed of a conjugated diene polymer,comprising one or more selected from the group consisting of butadiene,1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-methyl-1,3-pentadiene,1,3-hexadiene, 4,5-diethyl-1,3-octadiene, and 3-butyl-1,3-octadiene, orblock (B) is composed of a combination of isoprene and one or moreconjugated diene monomers selected from the group consisting ofbutadiene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene,2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, and3-butyl-1,3-octadiene, at least 80% of double bonds of the conjugateddiene moiety of the conjugated diene polymer block (B) is saturatedthrough hydrogenation, and a weight average molecular weight of (a) thehydrogenated (A)-(B) block copolymer and/or a hydrogenated (A)-(B)-(A)block copolymer is from 80,000 to 1,000,000.
 5. The laminated moldedarticle according to claim 4, wherein the styrene-based thermoplasticelastomer further comprises (b) a hydrocarbon softening agent forrubber.
 6. The laminated molded article according to claim 5, wherein acontent of the (A)-(C)-(A) triblock copolymer (c) is 20 to 300 parts bymass based on 100 parts by mass of the sum total of (a) the hydrogenated(A)-(B) block copolymer and/or a hydrogenated (A)-(B)-(A) blockcopolymer and (b) the hydrocarbon softening agent for rubber.
 7. Thelaminated molded article according to claim 6, wherein the styrene-basedthermoplastic elastomer further comprises: an olefin-based crystallineresin (d).
 8. The laminated molded article according to claim 7, whereina content of the olefin-based crystalline resin (d) is 10 to 100 partsby mass based on 100 parts by mass of the sum total of (a) thehydrogenated (A)-(B) block copolymer and/or a hydrogenated (A)-(B)-(A)block copolymer and (b) the hydrocarbon softening agent for rubber. 9.The laminated molded article according to claim 5, wherein based on 100% by mass of the sum total of (a) the hydrogenated (A)-(B) blockcopolymer and/or a hydrogenated (A)-(B)-(A) block copolymer and (b) thehydrocarbon softening agent for rubber; an occupying proportion of (a)is 20 to 80% by mass and an occupying proportion of (b) is 80 to 20% bymass.
 10. The laminated molded article according to claim 6, whereinbased on 100 % by mass of the sum total of (a) the hydrogenated (A)-(B)block copolymer and/or a hydrogenated (A)-(B)-(A) block copolymer and(b) the hydrocarbon softening agent for rubber; an occupying proportionof (a) is 20 to 80% by mass and an occupying proportion of (b) is 80 to20% by mass.
 11. The laminated molded article according to claim 7,wherein based on 100 % by mass of the sum total of (a) the hydrogenated(A)-(B) block copolymer and/or a hydrogenated (A)-(B)-(A) blockcopolymer and (b) the hydrocarbon softening agent for rubber; anoccupying proportion of (a) is 20 to 80% by mass and an occupyingproportion of (b) is 80 to 20% by mass.
 12. The laminated molded articleaccording to claim 8, wherein based on 100 % by mass of the sum total of(a) the hydrogenated (A)-(B) block copolymer and/or a hydrogenated(A)-(B)-(A) block copolymer and (b) the hydrocarbon softening agent forrubber; an occupying proportion of (a) is 20 to 80% by mass and anoccupying proportion of (b) is 80 to 20% by mass.
 13. The laminatedmolded article according to claim 1, wherein a concentration of anα,β-unsaturated carboxylic acid derived from the polymer modified by theα,β-unsaturated carboxylic acid in the thermoplastic elastomer is 0.01to 10% by mass.
 14. The laminated molded article according to claim 1,wherein a sliding material layer is contained on the surface of thethermoplastic elastomer layer on an opposite side to the carbon fiberreinforced plastic.
 15. The laminated molded article according to claim1, wherein the carbon fiber reinforced plastic comprises an epoxy resin.16. An automobile parts structure comprising the laminated moldedarticle according to claim
 1. 17. A shipping parts structure comprisingthe laminated molded article according to claim
 1. 18. A power partsstructure comprising the laminated molded article according to claim 1.19. A laminated molded article, comprising: a layer of a carbon fiberreinforced plastic; and a thermoplastic elastomer layer comprising: (a):a hydrogenated block copolymer which is a hydrogenated product of an(A)-(B) block copolymer and/or an (A)-(B)-(A) block copolymer composedof a vinyl aromatic compound polymer block (A) and a conjugated dienepolymer block (B) exclusive of isoprene alone, wherein at least 80% ofdouble bonds of the conjugated diene moiety of the conjugated dienepolymer block (B) is saturated through hydrogenation, and a weightaverage molecular weight of (a) the hydrogenated (A)-(B) block copolymerand/or a hydrogenated (A)-(B)-(A) block copolymer is from 80,000 to1,000,000; (b): a hydrocarbon softening agent for rubber; (c): ahydrogenated block copolymer composed of an (A)-(C)-(A) triblockcopolymer which is composed of a vinyl aromatic compound polymer block(A) and a conjugated diene polymer block (C), wherein the conjugateddiene polymer block (C) is constituted of isoprene, and a part or all ofcarbon-carbon double bonds based on isoprene are hydrogenated; and (d):a polymer modified by an a,β-unsaturated carboxylic acid; wherein aconcentration of the α,β-unsaturated carboxylic acid derived from thepolymer modified by the α,β-unsaturated carboxylic acid is 0.01 to 10%by mass.
 20. A method for bonding of a carbon reinforced plastic layerto a base material, comprising: laminating a thermoplastic elastomerlayer to a layer of a carbon fiber reinforced plastic; and bonding thethermoplastic elastomer layer to a base material; wherein thethermoplastic elastomer layer comprises: (a): a hydrogenated blockcopolymer which is a hydrogenated product of an (A)-(B) block copolymerand/or an (A)-(B)-(A) block copolymer composed of a vinyl aromaticcompound polymer block (A) and a conjugated diene polymer block (B)exclusive of isoprene alone, wherein at least 80% of double bonds of theconjugated diene moiety of the conjugated diene polymer block (B) issaturated through hydrogenation, and a weight average molecular weightof (a) the hydrogenated (A)-(B) block copolymer and/or a hydrogenated(A)-(B)-(A) block copolymer is from 80,000 to 1,000,000; (b): ahydrocarbon softening agent for rubber; (c): a hydrogenated blockcopolymer composed of an (A)-(C)-(A) triblock copolymer which iscomposed of a vinyl aromatic compound polymer block (A) and a conjugateddiene polymer block (C), wherein the conjugated diene polymer block (C)is constituted of isoprene, and a part or all of carbon-carbon doublebonds based on isoprene are hydrogenated; and (d): a polymer modified byan α,β-unsaturated carboxylic acid; wherein a concentration of theα,β-unsaturated carboxylic acid derived from the polymer modified by theα,β-unsaturated carboxylic acid is 0.01 to 10% by mass.